Decolorization of resins



Patented Feb. '16, i937 UNITED STATES.

PATENT OFFICE DECOLORIZATION or RESINS No Drawing.

Application November 16, 1934,

Serial No. 753,412

hydrocarbon resins and it has particular application to hydrocarbon resins of the type which are formed by the polymerization, under the influence of organic acid reacting catalysts, of unsaturated hydrocarbons. The present application is a continuation-in-part of our copending applications Serial Numbers 617,478, filed June 15, 1932, and 727,065 filed May 23, 1934. The present application is directed specifically to resins obtained by the polymerization of naphtha hydrocarbons of coal tar origin as, for example,

the so-called coumarone-indene type resin.

The object of the present invention is to .provide an emcient, economical and convenient method of improving the color of artificial resins derived from an unsaturated liquid hydrocarbon distillate obtained in the coking of coal and polymerized by acid catalysts, such as sulfuric 2O acid, aluminum chloride and/or. similar acict reacting substances. A further object of the invention is to simplify and condense the steps heretofore employed in the manufacture of hydrocarbon resins of the type herein under consideration.

Earlier methods have been proposed heretofore for the decolorization of coumarone-indene type resins. Howeventhese methods have not been entirely satisfactory and it has been customary rather to rely on careful selection of the raw materials to 'obtain a satisfactory polymerized product than upon a decolorizing operation which is employed after the polymerization, and it is therefore an additional object of our invention to provide a process wherein raw ma? terials of inferior quality may'be utilized successfully. In our copending application Serial Number 617,478, filed June 15, 1932, we have shown that polymerized hydrocarbon resins may be decolorized effectively by means of fullers earth or clay, preferably. of the so-called activated type, by fluxing the clay and the resin in the absence of solvent. To this end the resin, while melted is mixed with clay with rapid agitation and maintained at a relatively high temperature for a short period of time or a lower temperature for ya comparatively longer period of time. During this operation the water which is normally present in the clay is driven off and the fused mix- I ture then dissolved in a solvent whereupon the insoluble clay residue is separated from the resin solution. Alternatively, the fused mass may be solidified and pulverized before the addition of the solvent. A light colored solution is obtained in either case and the resin is recovered conven iently from the solution by evaporation of the solvent. v

There is also disclosed in the aforementioned application an alternative process wherein the polymerized hydrocarbon mixture which contains the acid polymerizing agent is neutralized and decolorized simultaneously. For example, the polymerized mass before separation of the catalyst is treated'with the activated clay whereupon neutralization is effected simultaneously with the decolorizatlon. The application likewise discloses a method wherein the resin which is neutralized is decolorized by means of activated clay while dissolved in a solvent.

In the copending application Serial Number 727,065 there is set forth a process wherein a solution of hydrocarbon resins such, for example, as coumarone-indene resin is heated to an elevated temperature with activated clay, preferably under reflux conditions, whereby the color imparting impurities are developed and thereupon are effectively removed from the solution. Aresin which is substantially free of color is thereby obtained.

The following detailed examples illustrate embodiments of our invention:

Example 1.--A coumarone-indene resin is dis-, solved in a suitable solvent as, for example, an aromatic hydrocarbon or alternativelya petro-- leum type hydrocarbon, to which there is added a finely ground activated bleaching clay. The suspension is. refluxed at from C.150 C. for, say, 15 to 30 minutes. For most coumaroneindene type resins this operation is performed effectively at temperatures of approximately C. Color producing constituents present in" the resin appear to be decomposed at about 125 C.

The materials which cause discoloration of the resin are thereby developed completely into an adsorbable form, adsorbed by the clay, and subsequently removed by the clay. Resinsof the described typesmay be effectively decolorized by the method of this invention at widely varying temperatures.

The proportion of clay used may be varied widely, amounts varying from 1% to 100% by weight of the resin treated, having been found effective. However, the decolorizing treatment has been found to be effective with relatively small amounts of clay, so that use of large proportions of clay is not recommended. Amounts 5 have been activated by a chemical process with acid, washed, neutralized, dried and ground. Two of these clays imported by the Harshaw Chemical Company of Philadelphia, and sold' under the designation Activated Bleaching Clay I H-l and"Activated Bleaching Clay H- have been found very satisfactory for this purpose. A domestic clay which is obtained in Georgia, known as Attapulgus clay, has been found to give very satisfactoryresults.

15 The resin solution may also be previously heated to a temperature of the order of 125 C. to decompose the color producing constituents, and the preheated solution then treated with clay at room temperature or at higher temperatures, as

described above.

After the above described treatment with clay, for example clay H-l or Attapulgus clay, the resin solution is separated from the clay by any convenient means, as by filtering. The color 2 bearing constituents of the resin and any'insolu- W ble materials remain with the clay, and the filtered resin solution is usually substantially colorless. If the color of the solution has not been lightened to thedesired extent, the clay treatment may be repeated using preferably a fresh batch of clay. The decolorized resin solution is then freed from solvent as by distillation...

leaving a hard colorless or very light straw colored resin. This resin is found to produce a clear varnish, and appears to be equivalent in chemical and varnish making properties to the resin produced in the same manner without the clay treatment. In lieu of .fullers earth or the special clays referred to hereinabove, one may employ a calcined clay, preferably one whichhas been heated sumciently high to remove combined water and thereby renderthe alumina present readily susceptible to the action of acids or acidic materials.

This decolorizing treatment may also be readily applied to the polymerized mass containing the resinous reaction product, at certain stages of the resin making process. For example, the polymerized mass at any time after polymerization may be. decolorized with a suitable. activated bleaching clay in the manner described above.

Example 2.'An acid polymerized coumaroneindene mixture is obtained preferably by causing a crude coal tar naphtha containing the' resin forming unsaturates having a boiling range of approximately 160-190 C., to polymerize in the presenceof any suitable acid reacting catalyst such as sulfuric acid while maintaining the reaction mixture preferably not substantially above 20 C. The reaction mixture, without previous .60 neutralizatio'n'yand which consists of the 1 polymerized resinous material dissolved in the unresinified coal tar naphtha which was present in the raw material, together with the sulfuric acid catalyst, is refluxed at"100-150 C. with finely 5 ground activated bleaching clay for approximately thirty minutes. The color producing constituents are thereby developed and adsorbed by the clay and the semis neutralized and/or otherwise adsorbed/by the clay. The proportion of clay ,70 may be varied. widely upto 100% by weight of the resin treated or even more. In general, the decoloriz'ation treatment has been found to beeifective withrelatively small amounts of clay sothat the use of large proportions of clay is not recommended; results are obtained by adding clay in the ratio of 1 to 5 grams of clay per 100 cc. of polymerized resin solution. The simultaneous neutralization and decolorization are mutually cooperative to effect not only complete neutrality but also a decolorization which is distinctly su- 6 perior as compared to decolorization obtained after neutralization, particularly when other desuitable. 20 I Example 4.In lieu of the treatments described 7 in the previous examples wherein a polymerized "resin of coal tar solvent origin is subjected to the action of clay while dissolved in a solvent, one can treat the resin while in a fluxed or liquid 25 state, containing little or no solvent, by mixing the vclay with the resin, preferably at a temperature sufllciently high to dry off water from the clay; for example, a temperature of the order of '200-2l0 C. for a period of 5 to 10 minutes will be foundeflective. Under these conditions the color impurity is developed while at the same time it is adsorbed by the clay. The resin in the fluxed mass is then dissolved in a solvent, for example,

hydrocarbon solvents of a petroleum origin or 30 hydrocarbons which are commonly associated with the resin forming constituents and the clay and other residue separated therefrom. Alternatively, the fused mixture can be cooled to effect: solidification and then pulverized, after which a 40 solvent is added. The insoluble matter is then separated by filtration.

A light colored solution is thus obtained from which the resin is recovered by'removal of the solvent. 45

Example 5.In Example 2 there is described a procedure wherein the acid catalyst is eliminated and the resin is decolorized more or less simultaneously by adding clay to the polymerized mixture. In the following example the polymerized 50 mass, preferably after dilution with one or more parts of a petroleum naphtha, is neutralized with a base such as caustic soda, after-which the color forming impurities are developed by the heat treatment described heretofore, and removed by- 55 means of clay. In this as well as the foregoing examples, the polymerization per'se forms no part of the invention insofar as the selection of a suitable polymerizing catalyst is concernedi A- large variety of catalysts are well known to those skilled 50 in the art, the most common one' of which is perhaps sulfuric acid due in part to its suitability and cheapness. It is to be understood, however, that the use of ,other'polymerizing agents falls within the s'piritof this invention. 5

Following the procedure outlined in the. preceding paragraph, a crude solvent coal tar mph: the; containing the coumarone-indene constitue ents isdiluted with from 1 to 4 parts of "petroleum naphtha and polymerized with a suitable catalyst.

such as sulfuricacid, under conditionswhich are well known to those skilled in the art. 'LAVIRFJE L polymerization is completed the reacted mixture is neutralized by agitating the same in the pressuspension is again heated to 125 C. for about a half hour, after which the clay is removed by filtration. Upon removal of thesolvent a decolorized, hardresinous product is obtained which is ready for sale or further use.

One should understand that in the foregoing examples the time of heating to develop the color forming impurities may be varied depending to a large extent upon the nature of the raw ma-'- terial being treated. Similarly it is to be understood-that the amount of clay required may. be varied according to the time of reaction, the effectiveness of the particular grade of clay employed, and the amount and nature of impurities tobe eliminated.

Although there have been set forth hereinabove a number of examples illustrating various embodiments of our invention according to which coumarone-indene type resins or resins derived from liquid coal tar naphtha fractions are polymerized and subsequently decolorized by treatment with clay, under various conditions which serve to develop the color forming impurities completely and render the same separable by the adsorptive action'of the clay, it is to be understood that the invention is not limited to the examples I specifically set forth but that it is susceptible to other variations without departing from the spirit thereof.

What we claim-is: i 1. The method of decolorizing a resin obtained by the polymerization of crude coal tar naphtha under the influence of an acidic polymerizing agent which normally results in an off-colored product, which comprises treating a preformed sorption in the clay of the impurities so developed and thereafter separating the clay from the resin. 2. The process'of claim 1 wherein the clay is an activated clay.

agent which normally results in an off-colored product, which comprises fluxing a preformed resin of this type with clay under heat conditions suflicient to render adsorbable the color-producing impurities associated with the resin and to provide for-complete adsorption in the clay of the impuritiessso developed, dissolving the resin in a solventlandseparating the insoluble clay from the solution and recovering the resin from the solvent.

5. The method of decolorizing a resin obtained .by the polymerization of crude coal tar naphtha under the influence of an acidic polymerizing agent which normally results in an ofl-colored product, which comprises dissolving a preformed resin of this type in a hydrocarbon solvent,.adding adsorptive clay to the sblution, maintaining the solution at a temperature of approximately ION-150 C. for a period of from approximately 15 to- 30 minutes in order to render adsorbahle the color-producing impurities associated with the resin and to 'provide for complete adsorption in the clay of the impurities so developed, separating'the clay from the solution and recovering the resin from the solvent.

6. The method of decolorizing a resin obtained by the polymerization of crude coal tar naphtha under the influence of an acidic polymerizing agent which normally results in an ofl-colored product, which comprises-reacting the resin with clay afterpolymerization and while the resin is still associated with the residual liquid hydrocarbons and the acid polymerizing agent to efl ect simultaneous neutralization and decolorization, separating the insoluble matter, and finally recovering the resin from-the! solvent.

'7. The method of decolorizing 'a-resin obtained by the polymerization of crude coal tar naphtha ".under the influence of an acidic polymerizing agent which normally results in an off-colored product, which comprises first neutralizing the resin after its formation, washing the same with water, subjecting the solution of resin to the devcolori'zation action of clay under heat, conditions which develop the colon and render the color-producing impurities adsorbable' by the decolorizing clay.

8; The process of claim 7'in which the polymerization and decolorization are eifected in the presence of a petroleum naphtha diluent.

v 9. The method of decolorizing a resin obtained by the polymerization of crude coal tar naphtha uhdenthe influence of an acidic polymerizing agent which normally results in an off-colored unneutralized product,. which comprises treating a preformed resin of this type. with clay, subjecting the mixture to heat conditions suflicient not only to neutralize the product by the clay but also to render adsorbable the color-producing impurities associated with the resin and to provide forcomplete adsorption in the clay of the irnpurities so developed and thereafter separating the clay from the resin.

. CHARLES A. moms.

WILLIAM csamonx. 

